Mercury compound of para-nitro-aniline and the process of making the same



Patented lien. 6, W31

UNITED ST TES PATENT OFFICE MORRIS S. KHARABCH, OF COLLEGE PARK,IIABYLAND, ASSIGNOB TO E. I. DU POINT DE NEMOURS & COMPANY, OFWILMINGTON, DELAWARE, A CORPORATION OF DELA- WARE MERCURY COMPOUND OFPARA-NITRO-ANILINE AND THE PROCESS OF MAKING THE SAME No Drawing.

zation o substitute anilines capable of forming stable salts in aqueoussolution, such anilines including the ortho, meta and para substitutedanilines. Any suitable substituted aniline of this type may be employed,for example, the chlor-anilines, the brom-anilines,

the sulfonic derivatives, the nitro-anilines,

etc. Of these I prefer in general to employ the nitro-anilines. I

In reparing the mercurized compound, the suhstltuted aniline of the typeset forth, for example, a para or meta nitro-aniline, is dissolved inwater together with suflicient acetic acid to keep it in solution, thepreferred proportion of acetic acid being slightly greater than thatcorresponding to a molecular equivalent thereof. The acidulated solutionof the substituted aniline is then heated to a moderate temperature,preferably below 100 0., for example, on a water bath, for two or threehours with an aqueous solution of mercuric acetate slightly acidulatedwith acetic acid, to prevent hydrolysis. The proportionof mercuricacetate employed is the calculated amount required to combine with theamount of substituted aniline present and is sufiicientto supply an atomof mercury for each molecule of the substituted aniline. Although it ispreferred that the mixture be moderately heated to accelerate thereaction, such heating is not necessary, as the reaction will also takeplace if the mixed solutions are allowed to stand at ordinary roomtemperature for long periods. The termination of the reaction isindicated when a test portion of-the solution fails to give aprecipitate of mercury sulfide with ammonium sulfide. Mercurization ofthe substituted aniline is then complete and the mercurized compound maybe removed in any suitable manner, for example, by crystallization, byprecipitation Application filed October 6, 1923. Serial No. 666,989.

as chloride, etc. For example, slightly more than a molecular equivalentof sodium chloride may be added in aqueous solution, the mercurizedcompound being then precipitated as the chloride.

This method of reaction is applicable to the substituted anilines of thetype set forth, that is, those capable of forming stable salts 1naqueous solution due to the basicity of the nitrogen. As a specificexample, the application of thereaction to para-nitro-aniline may begiven. The final compound has the formula NH: (\Hg0l It. is yellow incolor, powders readily, is only slightly soluble in Water; insoluble inether, somewhat soluble in alcohol and very soluble in acetone andpyridin.

138 parts by weight of paramitro-aniline together with 60 parts byweight of glacial acetic acid are dissolved in the minimum amountof hotwater required for complete solution, approximately 2,000 parts byweight being sufficient. A concentrated solution of mercuric acetate,containing 318.5 parts by weight of the latter, and slightly acidifiedwith acetic acid to prevent hydrolysis, is,

NO: The removal of the mercurized compound is most readily effected byprecipitation as 'the chloride, about parts by weight of sodium chloridein solution being added to effect the precipitation. Any other suitablemeans may be employed for the removal of the mercurized compound.Instead of using water solutions of the compounds mentioned a suspensionor paste of the products in which they are only partly dissolved may beused and treated in a manner similar to that of the water solution. Theisolation of the final product is effected exactly as in the case when awater solution is used.

The procedure described may likewise be employed in the mercurizing ofother substituted anilines of the type described, for example, meta andortho nitro-auiline, the corresponding chlor-anilines, brom-anilines,sulfo-anilines, etc. The precipitated mercurized compound, after dryingin any suitable manner, may be employed, either in water suspension oras a dry compound, as a germicide, fungicide etc., and by reason of itsrelatively low toxicity, it is particularly desirable for use in thetreatment of diseases of small grains, such as smut, wheat rust, and thelike.

The mercurized compound, for example, mercurized para or metachlor-phenol, a mercurized nitro-aniline, such as the mercurizedpara-nitro-aniline hereinbefore referred to, or other similar mercurizedsubstituted anilines, are admixed with inert substances such as talc,chalk, calcium sulfate or the like in proportions of from 5 to 15 percent, about 10 per cent being preferred. This mixture is then, in thetreatment of small grains, dusted over and thoroughly mixed with theseed grain, from 1 to 10 ounces of the mixture being used per bushel ofgrain. In general about two ounces has been found sufficient. Equivalentamounts of dilute solutions or suspensions may be employed; but the useof the dry mixture of the mercurized compound and an inert substance ispreferred, as it effectively destroys the various fungi without tendingto cause sprouting or germination of the grain. If it is desired to usethe substance in suspension in a liquid, an aqueous suspensioncontaining from one-half to eight per cent of the mercurized compoundmay be employed, about a one per cent suspension being preferred.

The compound may also be employed, in admixture with an inorganicfertilizer such as a phosphatic fertilizer, for the destruction of smutspores and similar disease producing organisms in the soil. In suchcase, the mercurized compound may be admixed with the fertilizer inproportions from one to ten per cent, about five per cent being thepreferred proportion.

Mercury compounds containing an HgX radicle attached to a carbon of asubstituted benzene ring, may likewise be employed for the treatment ofsurface diseases, such as scab and other external parasitic infectionsin potatoes, and in fruits of various kinds. They may be applied inwater solution or in suspension, or as dry substances, to the surfacesof the fruits or vegetables being treated in substantially the samemanner as in treating grains. All mercurized compounds having the groupHgX attached to a carbon atom of a substituted benzene ring may ingeneral be so employed. I

By the term aqueous medium, as used herein, I mean to include forexample a liquid medium, of which water comprises at lea st 60%.

I claim:

1. The method of producing mercurized organic compounds which consistsin reactmg upon an acetate of a para-nitro-aniline with mercuricacetate.

2. A mercurized nitro-aniline of the general formula RHg-Cl, in which Rrepresents a nltro-aniline nucleus to which Hg is attached through acarbon atom.

3. The method of producing mercurized organic compounds containingmercury attached to a carbon of a substituted benzene ring whichconsists in reacting upon an aqueous solution of an acetate of asubstituted aniline capable of forming stable salts in a non-alcoholicaqueous solution with mer- CllIlC acetate.

4. The method of producing mercurized aromatic amines containing mercuryattached to a carbon atom, which consists in causing a mercuric salt toreact on an amine 111 a non-alcoholic aqueous medium.

5. The method of producing mercurized aromatic amines containing mercuryattached to a carbon atom, which consists in causing a mercuric salt toreact on a. saltformmg aromatic amine, in a non-alcoholic aqueousmedium.

6. The method of producing mercurized aromatic amines containin mercuryattached to a carbon atom, w ich consists in causing a mercuric salt toreact on a saltforming aromatic amine, in a non-alcoholic aqueousmedium.

7. The methodof producing mercurized aromatic aminescontaining mercuryattached to a carbon atom, which consists in causing a mercuric salt toreact on a saltforming aromatic amino in a non-alcoholic aqueous mediumand in the presence of acetic acid.

8. The method of producing mercurized aromatic amines containing mercuryattached to a carbon atom, which consists in causing mercuric acetate toreact on a saltforming aromatic amine, in a non-alcoholic aqueous mediumand in the presence of acetic acid.

9. The method of producing mercurized aromatic amines containing mercuryattached to a carbon atom, which consists in heating together a mercuricsalt and a saltforming aromatic amine in a non-alcoholic aqueous medium.

10. The method of producing mercurized aromatic amines containingmercury attached to a carbon atom, which consists in causing a mercuricsalt to react on a substituted salt-forming aromatic amine, in anonalcoholic aqueous medium.

11. A mercurized para-nitro-aniline of the formula in which Hg isattachedto a carbon atom.

MORRIS S. KHARASCH.

